Journal of the American Chemical Society
COMMUNICATION
step under aqueous basic conditions. This is followed by the base
induced elimination (dehydrohalogenation) of corresponding
chlorosulfonate at higher temperatures to generate vinyl sulfo-
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coupling catalytic cycle to give the desired Heck-coupled product
in an overall three-step reaction.45
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To make proton exchange membranes/electrolytes for fuel
cell and battery applications, we intend to synthesize ethane
sulfonate salts, which can be accessed by hydrogenation of the
styrene sulfonate salts obtained in Table 1. We were able to hydro-
genate46 compounds 1, 11, and 14 (see Supporting Information) to
obtain the corresponding ethanesulfonate salts in excellent
yields.47 Further application of this novel Heck coupling method
to synthesize polymeric materials containing ethanesulfonate
salts is underway.
In summary, we have shown that various styrenesulfonates can
be synthesized by a novel domino approach, where the alkene is
made in situ prior to Heck coupling. This synthetic protocol is
quite environmentally friendly as it involves phosphine free
catalysis, water as a solvent, and it does not require addition of
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’ ASSOCIATED CONTENT
S
Supporting Information. General experimental proce-
b
dure along with spectroscopic data of all products. This material
’ AUTHOR INFORMATION
Corresponding Author
(30) Yolacan, C.; Bagdatli, E.; Ocal, N.; Kaufmann, D. E. Molecules
2006, 11, 603–614.
(31) Giguere, D.; Patnam, R.; Juarez-Ruiz, J. M.; Neault, M.; Roy, R.
Tetrahedron Lett. 2009, 50, 4254–4257.
’ ACKNOWLEDGMENT
Financial support for our work by Loker Hydrocarbon Re-
search Institute is greatly acknowledged. Dr. M. Czaun is thanked
for useful discussions.
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(45) Heating the reaction mixture containing only chloroethanesul-
fonyl chloride and K2CO3 (2 equiv) at 180 °C for 10 min in microwave
produced potassium vinyl sulfonate (by 1H NMR). Addition of
palladium(II) acetate, iodobenzene, and 1 equiv of K2CO3 to the same
reaction mixture followed by heating under identical conditions gave 1 in
82% yield.
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